Disazo- and polyazo-dyestuffs and complex metal compounds thereof and process for their manufacture



a 2,824,865 1C6 Patented Feb-25,195

United States Patent 6 I diazoor diazoazo-compound being, used which contains 2,824,865 in ortho-position to the diazo group a group capable of forming complexes. gfigg' m The naphthalene derivatives to be used as coupling PROCESS FOR m MANUFACTURE components correspond to the general formula Oskar Weber, Reinach, Walter Anderau and Raymond (4 I Gunst, Binningeu, and Bernhard Ruetimeyer, Neuali- Q V I V schwil, Switzerland, assignors to Ciba Limited, Basel, NH -alkylene-SWH Swit'zerland,aSwissfirm V a 10 No Drawing. Application August 29,1955 i h V SerialNo. 531,256 ,7 s, V 7

Claims Priority, Pllication Switzerland in whichfthNH-alkyliene-SQH group occupies a 18 a 7 septembe! 2,1954 a pes qno en phthalene ring. of special advantage in q'c (CL z V the present process are those derivatives, in which only one 7 carbon atom of 7 the .alltylene radical is between the This invention provides new disazoand polyazo-dye- .H dj h aH: P and especially those in stufis of the type of the dyestuff of the formula whichltlie alkylene radical consists only of a-CH -group.

(1) a a a mN soan no3 nrr-onr-sosu no on no H and complex metal compounds thereof, for example, com- Such derivatives are easily obtainable by reacting an' applex copper compounds of the type of the formula propriate amino-hydroxy-naphthalene sulfonic acid with HiN SOaH HO: NH-CHa-SOzH o--ou-'0 n-cu-o v V These dyestuifs correspond to the general formula the addition" compound of formaldehyde withean alkali (3) 7 metal bisulfite. i

As diazo-compounds, which may contain one or more 40 directly when coupled with the'aforesaid coupling com- V y 0: azo linkages, and'thus yield disazo'or polyazo-dyestuffs ponents, there are-used in the present process those which V s OH con tain in ortho-position to the coupling diazo-groupa in which the NH-alk ylene-S O H group occupies a 3- group capable of forming complexes, especiallyahydroxyl position,-RN=N represents the radical of a diaz0-, g p, carboxyl g p, a z p 'v an compound containing in ortho-position to the diazo group Y group, which advantageously domains an a y agroup capable of forming complexes, and the radical R radical f low molecular h w p of represents a radical containing at least one further azo i yielding by metallization, if desired, with the splitting oft linkage. of-the alkyl radical, for-example, an'orthozorthd-dihy- The invention also provides a process for the manufacdI XY- -g HPiBg in he 'metall z d C nditi n. AS 67(- ture of dyestufis of the above Formula 3'by a method in itamples of such diazocompounds there may be used chain self known by using as a coupling component a l-hydroxydyestuifs, which are obtained by coupling diazotized naphthalene-3-sulfonic acid which contains an amino flm fl y acid a p y a group in a fi-position of the ring not containing the hysulfonic acid, for example, adehydrothiotoluidine-sulfonic', droxyl group, and a diazo-compound which contains in aCiQJ/ith amiddle component, for instance amiddlecoma position vicinal to the diazo group a group capable of ponent of the benzene series, and further diazotizing the taking part in the formation of complex metal compounds, amino-azo-dyestuff so obtained. There may be" used as 1 if desired, treating the dyestuff with an agent yielding middle components amines of the benzene ornaphthalenemetal and, if the dyestufi contains only a single azo-linkseries, which couple in para-position to the amino group age, linking a second dyestufi molecule to a nitrogen-conand contain inortho-position to the amino group a sub-- taining substituent, wherein in the course of the preparastituent capable of forming complex metal compounds, tion of the dyestufi the amino group present in' the aforefor example, l-amino-2amethoxy-S-methylbenzene or 1-, said coupling component is treated with an agent capable aminobenZene-Z-carboxylic acid. of converting the amino group into an N-alkylene-sulfonic In the present process tetrazotized 4:4'-diamino-diacid group. phenyl compounds are especially valuable which'contain The amino group may be converted into an N-alkyleuein the 3- and 3f-positions a group capable of forming meta sulfonic acid group, for example, before or after the complexes, for example, a'car'boxyl group, an coupling. a Y

Thus, the dyestuffs can be made with advantage in this C e a 1 a yr; manner by using as coupling-components at least once a group or especially a methoxy or-hydroxyl group. i It is 1-hydroxynaphthalene-3-sulfonic acid which contains an especially simplefto manufacture disazo-dyestufis by-- -N-alkylene-sulfonic acid group in a p-position of the starting from tetrazo-compounds sincesthese teu'a'zo-com-e ring not con ain ngrthe hydroxy g oup, and at leastones pounds. may be o pl d. wi hwtwo identical, or different:

'the Formula 4, the corresponding aminohy'droxynaphthacouplingrcomponentsof the Formula 4 or ,with anytjde V i sired coupling component, advantageously one capable series'or apyrazolone, and withia coupling .component'of" 5 the Formula 4. a

' -Further valuable dyestuffs can be 'madeibyithezpreseut processby couplingacompound of. the. Formula 4.with'. a diazo-cornpoundlwhich contains in ortho-position to the diazo group agroup capable of forming-metal complexes pi'odu'ctof formaldehyde and dicyandiamidine'and si 'nil p :as aforesaid and, advantageously inthe para position to :the diazo group, a'fu'rther nitrogen-containing substituent, for example, a nitro or acetylaminogroup, and then linking together at this nitrogen-containing substituenttwo molecules of themonoazo-dyestufi so obtainedor one molecule'of such dyestufi and one molecule ofanother:

for example, dyestufls containing gnitro groups maylrbe" treated with mild reducing agents,advantageously'with per-containing dyestuifsflare used or the dyestuffs are V coppered'on the fiber, fastdyeings, and especially dyeings fast to washing and light,? whieh, .if desired,'m'ay be subjected toanafter-treatment and further improved-intheir...

properties of. fas'tness, 'As after treatmentsg ther'e come? into consideration an anti-creasing treatment withfafureaformaldehyde resin, and a treatment with a condensation;

products. e I

r, V ,Exqritpll a 21.6 parts of 3,:3' dihydroxy-4i4'diarninodiphenyl are tetrazotized in the usual: manner: The "-neuh'ali'zed I and "filtered tetrazo-compound is 'introducedat 5-1.0 C. into glucose in an'aqueous solution ofan alkali metalhydrox-* Q di'oxynaphthaleneJ-sulfonic 80 Pa ts of anhydrous ide, .whereby linking together'of the monoazo-dyestuffs g 7 containing nitro groups'takes place with the formation'of an azoor azoxy-linkage. V

' Alternatively, in the monoazodyestufis obtainedas de-.,

sodium carbonate, 100 parts of pyridineand .800partsof water. Therexare .also; -added,:.50 parts of copper sulfate in '200parts of concentrated ammonia solution. After? a few hoursthe'coupling is complete, and the coppercomscribed above the nitro groups maybe reduced to amino 2 Poundfifthe disazo'dyestufi-is filtered 3011" T PY d means of phosgene into urea derivatives or by means of 'cyanuric chloride into aminot'riazine derivatives, ,it being,

used can then beregeneratedin' known manner.

The drydyestuir' is a dark powder which .tdis'solves in concentrated sulfuric acid with'a blue .green coloration It "dyes cotton and regenerated cellulose pure blue'tintsj possible by linking together two ditt'erent'monoazof-dyea y-89 fasmss to light'andvwashil'lrgil Inf} stufis to'produ ce disazo -dyestufi'sof 'a symmetrical consti tution. 7 As already mentioned, the disazoand polyazo-dyq;

stutfsobtainable in the manner described above can also The same dyestufi can :be obtained as follows:

21.6 parts of '3:3f-dihydroxy 4z4' diaminodiphenyl arer be' obtained by using, instead of coupling components of, 5 of 3 1 *hY IQ Y P I iS Q i acid? when lene sulfonic acids unsubstituted at the nitrogen atom and introducing the. -NH-alkylene-SO H group after.

. -coupling,.for example, immediatelyafter couplingor if a V a desired, after linking the ,mouazo-dyestufisj together. 40 hydroxl'de- An aqueous solutlon'of Parts of'formal Thu s, a disazo,.orpolyazmdyestufli, for example, whichis obtainable "by using as coupling componenta l'-hyd r'o xy- 'naphthalene-3-sulfonic acid containing an'amino groupj ina'fi-position of theriug not containing the hydroxyl' group and 'atleastone diazm or diaz o-azo compoundj w r, g

' trated ammoma and SOpartsof crystalhne'copper sulfate V are added. Aiter' stirring 40it is"-filtered.' 1

which contains a group capable of forming complexes in ortho-position to the "dia'z'o group, isttreatedwith agent'capable' of converting'the' amino group into anN- f.

alkyl-sulfonic acid group; As such agents there may, be

30 percent strength and filtered ofi. Thejdyes'tuifpaste; is then neutralized with a concentratedsolution of sodium dehyde and 20,8 parts of sodium bisulfite are then added,

and. the mixture is'heatedfor 2 hours at 85 C. When the condensation is finished, the temperature is allowed K tofallto40C v For the purpose'of metalli'zation 60 parts of concen- V The dried'dyestufi has the properties described in the used, for example; fl-chlorethane su1fonic'.acid-, but p p f this m l especially the above-mentioned additioncompounds of al I dehydes, advantageously formaldehyde, with'bis'ulfites.

"Th'e' disazoand polyazo-d'yestutfs obtainable as defscribed above can be converted in the usual manner on the fiber, in the dyebathor especially'in su bstanceinto Y following thprocedule dscribedinfthe first P 7 their complex metal compounds, for'example,complex; ch'romium,"cobalt, nickel and especially copper com= accompanied by the splitting off of the alkyl-group 'of'the diazo-component, for example, by prolonged heating with i an ammoniacal solution of a copper salt or by using a processinwhichthe heating with a copper'comple'x is carried out in the presence-of ethanolamine. v ,In' some cases, for example, when tetrazo-compounds of"3':3'-dihydroxy-4:4'-diaminodipheny1 are used, it is of .l

advantage to add-to the coupling mixture an agentyieldfing metal, especially an agent yielding copper.

methylamino)-8 hydroxynaphthalene 6-sulfonic" acid;

graph of this example, but, using,'instead*of copperjsul fate, a corresponding quantitybf nickel sulfate 'there'is" obtained'a dyes'tufffwhich. dyes-{cotton somewhat more 'reddish'lbluetints than the copper-containing:dyestuif.

-21 .6 parts 0533 3.. dih'ydroxyf' 4154' diaminodiphenylf are tetrazotizedtin .the' usual manner andthe llIEZO-xf suspensioncis :neutralized land the tetra2o compound -fil- 5 tered1off. .The :sd-obtainedpaste-is then introduced at} 10 1590. intozai-suspension of .66.6 parts 'of 2-(sulfomethylamino)-5 hydroxynaphthalene-7-sulfonic acid, 296- parts of icalcium'hydroxide od parts of pyridine and 80 0 parts of.;water. qWhen thereaction is'fini'shed,jthe pyri The dyestufis of this inventionand their complex metal dine" is distilled off a h x p mixturermainingecompounds, especially their complex copper compounds aresuitable for'dyeinga very wide' variety-offmaterials,

for example-animal fibers such" as wool or leather; but especially for dyeing or'printing fibrous materialsxof hat-.

behindismixed withl a solution of.35 parts of anhydrous sodium-carbonateJim-35d parts of water, the mixture I is filtered;to' nemove icalciumzcarbonate; and the dyestuti'gis 5 metallized by the addition of .50 parts or copperfsulfate f ural'.orrregenerated.zcellulose; suchzasscottom'linen; and .76 in y200=parts.ofir'concentratediammoniaesolutioni After :the 'mixture tor one hour at A dyestutf which'dyes cotton and regeneratedcellulose I stirring the mixture for one hour at 40 C., the copper compound of the disazo-dyestufi issalted' out and filtered; off. The dried dyestuff has the properties described in the second paragraph of Example 1. j

5 V m l 3 r 24.4 parts of 3:3-dimethoxy 4:4'-diaminodiphenyl are dissolved in 300 parts of water with 25 parts of hydrochloric acid of 30 percent strength. After the addition of a further 25 parts of hydrochloric acid tetrazotization is brought about at- 25- C. with 14 parts of sodium nitn'te. The clear solution of the tetrazo-compound is run at -5 C. into a solution of 66.6 parts of 2-(sulfomethylamino)--hydroxynaphthalene-7-sulfonic acid and 80 parts of sodium carbonatein 300 parts of water. After 15-20 minutes the reaction is finished; The mixture is then heated to 70 C. and the dyestuff is filtered off.

The dyestufi paste so obtained is diluted with 700 parts of water, the mixture is heated to 80 C., and a solution of 50 parts of copper sulfate in 200 parts of concentrated ammonia solution isadded. After stirring the mixture for hours at 80-85 C., the metallization is complete and the new dyestuff is salted out and filtered off. It has the same properties as the corresponding dyestuffs described in Examples 1 and 2.

Example 4 21.6 parts of 3:3'-dihydroxy-4:4'-diaminodiphenyl are tetrazotized in the usual manner, and the neutralized and filtered tetrazo-compound is introduced at 0-5 C. into a mixture of 23.9 parts of Z-amino-S-hydroxynaphthalene-7-sulfonic acid, 40 parts of sodium carbonate, 120 parts of pyridine and 800 parts of water. The whole is stirred overnight and the next day the diazo-azo-compound is filtered off, and the paste so obtained is coupled with a solution of 33.3 parts of 2-(sulfomethylamino)-5- hydroxynaphthalene-7-sulfonic acid, 60'parts of sodium carbonate, 120 parts'of pyridine, 50 parts of copper sulfate, 69.parts of concentrated ammonia solution in 600 parts of water. After stirring for several hours at room temperature, the coupling is complete and the new dyestufi is filtered off. The dried cupriferous dyestufi' is a dark powder which dissolves in concentrated sulfuric acid with a blue-green coloration. It dyes cotton and regenerated cellulose blue tints of very good fastness to light and washing.

Example 5 By using in Example 4, instead of 2-amino-5hydroxynaphthalene-7-sulfonic acid, 2-hydroxynaphthalene-3:6- disulfonic acid, there is obtained a similar dyestuff which dyes cotton and regenerated cellulose reddish blue tints of very good fastness to light and washing.

Example 6 added, and the whole is stirred for a further 2-3 hours.

at room temperature.

In order to convert the dyestutf into its complex copthe whole is stirred for 6 hours at 95-100" C. underre- By the addition of sodium chloride and allowing 4 flux. the mixture to cool, while stirring, the copper complex of the dyestufi so formed separates out andcan belfil tered off and dried.; It is a darkpowder which dissolves' in water with a grey-violet coloration and dyes cellulose: fibers bluish grey tints which are fast to light.

7 Example '7 32 parts of 2-(4-aminophenyl)-6-methylbenzthiazole sulfonic acid (obtainable bysufonating 2,-(4'-aminophenyl)-6-methyl-benzthiazole with concentrated sulfuric acid) are dissolved in the form of the sodium salt in 200 parts of water, and 6.9 parts of sodium nitrite are added. The solution is slowly run into a mixture of 30 parts of. hydrochloric acid of 30 percent strength, 100 parts of water and 100 parts of ice. The whole is stirred for one hour, and then the suspension of the diazo compound is introduced into a solution of 21.7 'parts of 1-amino-2- methoxybenzene-w-methane sulfonic acid, whichsolution contains an excess of sodium bicarbonate, and the whole is stirred at 10 C. until the coupling is complete. The monoazo-dyestutf is then separated ofi,'and hydrolyzed by heating it for one hour at C. with a dilute solutionv of sodium hydroxide. The'amino-monoazo' dyestuif isseparated from the mixture, dissolved in water with the addition of sodium carbonate until the reaction is weakly alkaline, then 7 parts of sodium nitrite are added, and diazotization is brought about by pouring in 30 parts of hydrochloric acid of 30 percent strength. The whole is stirred for 2 hours at about 45 ;C., and the diazo-compoundiscoupled in a solution rendered alkaline with sodium carbonate or sodium bicarbonate with 33.3 parts of 2 (sulfomethylamino) 8 hydroxynaphthalene 6 sulfonic acid. Coupling is strongly accelerated by the addition of a small amount of pyridine. or picoline. When the coupling is finished. the disazo-dyestufi is salted out and filtered off. a

The dyestutf paste is dissolved in 1500 partsof water with the addition 30 parts of monoethanolamine, and the solution is mixed with an ammoniacal solution of copper sulfate (corresponding to 27.5 parts of CuSO .5H O). The treatment is carried out for 4 hours at C. under reflux. The complex copper compound so obtained is salted out, filtered off and dried. There is obtained a grey powder, which dissolves in waterwith a grey coloration, and dyes cotton greenish grey tints which are fast to light.

Example 8 compound, which is added to an ice-cold solution of 35 parts of 2-(sulfomethylamino)-5-hydroxynaphthalene 7-- sulfonic acid and 50 parts of anhydrous sodium carbonate in 600 parts of water.

After heating the mixture for 2- hoursat 65 C., 90 1 parts of sodium hydroxide solution of 30 percent strength are added, and then a solution of l717.8 parts'of dextrose in 60 parts of water is added. A color changeoccurs. After 10 minutes there are added 110 parts of sodium bicarbonate and also 200 parts of sodium chloride, whereupon the dyestutf precipitates. It is filtered off, and the filter paste isdissolve'd in 700 parts of water at 70. C.. and .70 parts of ammoniasolution of 24-percent strength and an aqueous solution of 25 parts of crystalline copper sulfate are added. The whole is stirred for 6 hours at 85-90 C., parts of sodium chloride are added, and the dyestuff obtained by this demethylating coppen'ng treatment is filtered off and dried in vacuo at 80-90' C.

There is obtained a blackish powder, which dissolves in water and in dilute alkalies with a'grey-blue coloration.

It dyes vegetable fibers and artificial fibers of regenerated cellulose grey tints which are very fast to light.

7 Example 9 18.2 parts'of S-nitro-Z-aminobenzene-l-carboxylic acid are dia'zotized indirectly in the usual manner. diam. 1P i 93 l p Q idi thi u e n 'i n at "G. into. a mixtu e o 3 -3 ipa fi e' dje fi l fP tei hi ip z mbl d ci sis of'Z-(suIfomethyIamind) 8 hydroxynaphtha1ene-6-sulfonic V ea ned on hlle ral gthe tempe ature o 0 Q d acid, 32 parts" of ammonium carbonate and '200 parts of 30 parts of crystalline podium sulfate [are added,- and water while the pH value is'kept constant at 7.8-8.1 by the 5 dye ng 1s continued forga further /z hour at 90-95 ,C.

' ad ition of. so ium hydroxide solution of all) percent The cotton is then rinsed and finished in the usual man- J r V is salted out and-when dry is a dark brown powder. What is claimed is:

strengthl After 2-3 hours the coupling is finished and net. 'It is dyed a pure blue tint and the 'dyeinghasia;

the dyestufi partially precipitates. The m-onoago-dyestufi very good fastness to light and washing. V 52,.6 parts or the resulting monoazq dyestufi containing .1 1. A metalliferous azo-dyestuff of the formula. V a nitror group are dissolved in 1000 parts of; water at 50 C; 40 parts of sodium hydroxide are. addedin the 1 1 a 7 7 immediately poured in in one portion 100 partsby volume A te a r n time; of i utes tSO-QQ? (L; th dyest .0 minutes y h d iti n of SQ iU 'Qh D idQ-J T e;

form of a solution of percent strength, and there are ofta solution of dextroseof 10 percent strength at; 60 C.

stufi' partially precipitates out. 150 parts, of, sodium-121' a on a dd and t e dy s ufi; i-Pre p tated mixture is filtered'at -50 C. The dried-dyestuffi is. a 0 in which -group occupies a fldark powder which dissolves in concentrated :SU fUIiQ position and r 7 acid with a blue-green eoloration Itdyes, cottonqand regenerated cellulose reddishviolet-grey tints,which -whjen 7 E trcatedwith an agent yielding copper change to'a neutral p M grey offgood 'fastness towas hing and lights ;f 7

1:1'-.dipl 1enyl. are tetrazotized in the usual 'mannen-and treated with a 'solution, rendered alkaline; with; sodium 3(l I an hour, the symmetrical dyestufi is salted out fwitl igglji carbonate; of 66.6 parts of 2 sn1r m th i nain 2). atheist-par d hydlfoxynaphthalene-fiaulfonic acid,inr 0 partso f; ater; t v V e t r and 35 parts, of; sodium'ca'r bonate at 0? C2,: -A fteiz hal-fi i V r sodium chloride. e V t r p 35 I The product'is a dark .hlue'powder which dissolves in concentrated sulfuric acid, with 'a clear blue-colorationand dyes cotton and'regenerated cellulosen blue tints In the form of the free acid it corresponds to the formulia p ti m T 00011 V zanyar of 'th' afdrenientibndiu angsta-lain; and the formcfthe'sodium saltg'aredis'solvedin (10" parts of? water at so '0. There" are added areby drep heif course 0f n 1 11 3 59 10? p r s r' i s' aqueous copper sulfate;'dissolved'in' 1G0 partsffof nd lp rts of concentrated ammoniai'and' 10 ethanolamine'. Copperingis complete. after 1 After'neutrali'zatidn Qfthe medium the'dyfe'stuff' v out-with- I 0%'-'-sodiu'm chloride; It i'st aidark, rathl ficultly soluble powder haying a metallic luster andfl cotton and regeneratedcellulose. slightly bluish gr'eyf of-i'gcodifastnessi' i '1 t benithiaiole sulfbhic acid; represents" a eenzenaraui:

a e v f tionto thea'zolinkag'es; V 7 V V U partsr'of cottomare'gentered ;at-40V Ggintoahath 2-.'-Acupriierous',azo dyestufitoffthe formula represents: a; radical selected from we group consisting V the adical 7:61? a Z -(aminophenyl cal-X repfseiits a-member selected"- frcii1 1 the group eon;

V sisting of azoand-'zazoxy groups' Met'representsia metal t havinganatomic?number-Qof at least 28 andjat the I i mi f r f '60 most 29 arid all-theO -'Me' groups areiin'ortho-posi 7 mmm soti linkage in ortho-position to the -O-Cugroup, and in which X represents a member selected from the group the -NH-CH --SO H group occupies a fi-position.

5. A cupriferous azo dyestufi of the formula S03 HOaS HOaS CHrHN NHOH;SO:H

| O--Cu0 0 Cu0 consisting of an azo group and an azoxy group. 10

4. A cupriferous azo dyestuft of the formula HOaS NH-OH -SOQH b th RrN=N m 15 in pvhlch 0 NH CH SO H groups occupy p I I positions.

o--ou--0 0ou0 6. The cupriferous azo dyestuft of the formula in which R represents a naphthalene radical containing ---Cu O OOu-O at least one sulfonic acid group and bound to the azo- 7. The cupriferous azo dyestutf of the formula HzN SOaH HOsS NH-C'Hr-SOaH References Cited in the file of this patent UNITED STATES PATENTS 2,630,431 Trepagnier Mar. 3, 1953 FOREIGN PATENTS 276,905 Switzerland July 31, 1951 

1. A METALLIFEROUS AZO-DYESTUFF OF THE FORMULA 